Synthetic polymers having hydrogen bonding capability and containing aliphatic hydrocarbon moieties

ABSTRACT

Synthetic polymers having hydrogen bonding capability and one or more aliphatic hydrocarbon moieties are capable of providing two distinct properties to paper products, such as tissues, which properties heretofore have been imparted through the use of at least two different molecules. The backbone of these synthetic polymers is based on modified vinyl polymers, such as polyvinyl alcohol, polyacrylamides and polyacrylic acids.

This application claims benefit of Provisional Appln. No. 60/117,167filed Jan. 25, 1999.

BACKGROUND OF THE INVENTION

In the manufacture of paper products, such as facial tissue, bathtissue, paper towels, dinner napkins and the like, a wide variety ofproduct properties are imparted to the final product through the use ofchemical additives. Examples of such additives include softeners,debonders, wet strength agents, dry strength agents, sizing agents,opacifiers and the like. In many instances, more than one chemicaladditive is added to the product at some point in the manufacturingprocess. Unfortunately, there are instances where certain chemicaladditives may not be compatible with each other or may be detrimental tothe efficiency of the papermaking process, such as can be the case withthe effect of wet end chemicals on the downstream efficiency of crepingadhesives. Another limitation, which is associated with wet end chemicaladdition, is the limited availability of adequate bonding sites on thepapermaking fibers to which the chemicals can attach themselves. Undersuch circumstances, more than one chemical functionality competes forthe limited available bonding sites, oftentimes resulting in theinsufficient retention of one or both chemicals on the fibers. For morecomplex chemical systems it may desirable to have two or more functionaladditives retained in a specified ratio and/or spatial arrangementrelative to one another. Although the addition of chemicals in apre-determined ratio is easily achieved, retention of these chemicals ina predictable ratio is difficult using wet end chemical addition becauseof site competition and other influencing factors. Another limitation ofeither wet end or topical chemical addition is the inability topredictably locate functional chemical moieties in proximity to eachother on the fiber surface.

Therefore, there is a need for a means of applying more than onechemical functionality to a paper web that mitigates the limitationscreated by limited number of bonding sites and the unpredictable natureof chemical additive retention which limits the ability to retainfunctional groups in a specified ratio and/or spatial arrangement withrespect to one another.

SUMMARY OF THE INVENTION

In certain instances, two or more chemical functionalities can becombined into a single molecule, such that the combined molecule impartsat least two distinct product properties to the final paper product thatheretofore have been imparted through the use of two or more differentmolecules. More specifically, synthetic polymers, which are commonlyused in the paper industry as dry strength resins, wet strength resinsand retention aids, can be combined into a single molecule with modifiedaliphatic hydrocarbons, which are commonly utilized, in conjunction withcationic moieties, as softeners, debonders, lubricants and sizingagents. The resulting molecule is a synthetic polymer having hydrogenbonding capability and an aliphatic hydrocarbon moiety which can provideseveral potential benefits, depending on the specific combinationemployed, including: (a) strength aids that soften; (b) softeners thatdo not reduce strength; (c) wet strength with improved wet/dry strengthratio; (d) debonders with reduced linting and sloughing; (e) strengthaids with controlled absorbency; and (g) retention aids that soften.

As used herein, “aliphatic hydrocarbon moieties” are functional groupsderived from a broad group of organic compounds, including alkanes,alkenes, alkynes and cyclic aliphatic classifications. The aliphatichydrocarbon moieties can be linear or branched, saturated orunsaturated, substituted or non-substituted.

The synthetic polymers as described herein, have a portion of theirstructure derived from the polymerization of ethylenically unsaturatedcompounds which contain pendant groups that can form hydrogen bonds,ionic bonds or covalent bonds with cellulose molecules in fibers,thereby increasing interfiber bonding. They include polyacrylamide,polyvinyl alcohol, polyacrylic acid, polymaleic anhydride, polymaleicacid, polyitaconic acid, cationic polyacrylamides, anionicpolyacrylamides, and the like. The synthetic polymers as describedherein may be water soluble, organic soluble or soluble in mixtures ofwater and water miscible organic compounds. Preferably they arewater-soluble or water dispersible but this is not a necessity of theinvention. Also included within the definition are the salts of theabove mentioned acidic polymers. Substances which can be combined withthe acidic portion of the polymers to make the salts include the alkalimetals such as K and Na usually added in form of their hydroxides, thealiphatic amines and alkanol amines, such salts and methods of preparingsuch salts being well known to those skilled in the art.

Depending upon the chemical and the desired impact on the paper sheet,the synthetic polymers of this invention may be applied to the paper webby any of the means known to those skilled in the art. Such meansinclude wet end addition, spray addition on the wet web, as a crepingchemical sprayed on the Yankee dryer, or as a post treatment addition,including spraying, printing or coating.

Hence in one aspect, the invention resides in a synthetic polymer havinghydrogen bonding capability and containing one or more aliphatichydrocarbon moieties, said synthetic polymer having the followingstructure:

where:

a, b>0;

c,d≧0 such that c+d>0;

w≧1;

Q₁=a monomer unit or a block or graft copolymer containing a pendantgroup capable of forming hydrogen or covalent bonds with cellulose.Preferred pendant groups for hydrogen bonding are —CONH₂, —COOH,—COO⁻M⁺, —OH and mixtures of said groups. Preferred pendant groups forcovalent bonding are aldehydes and anhydrides. M⁺ can be any suitablecounter ion including Na⁺, K⁺, Ca⁺² and the like.

Q₂=a monomer unit or a block or graft copolymer containing a C₈ orhigher linear or branched, saturated or unsaturated, substituted orunsubstituted aliphatic hydrocarbon moiety. Q₂ may take the form of—Z₁—Q₂—Z₁′— where Z₁, Z₁′ are any bridging radicals, the same ordifferent, whose purpose is to provide incorporation into the polymerbackbone and Q₂ is as defined previously;

Q₃=a monomer unit or a block or graft copolymer containing a chargefunctionality. Such charge functionality is preferably cationic but maybe anionic or amphoteric; and

Q₄=a monomer unit or a block or graft copolymer containing a hydrophilicmoiety, which is desirable for making the material into a form suitablefor papermaking. Q₄ may take the form of —Z₂—Q₄—Z₂′— where Z₂, Z₂′ areany bridging radicals, the same or different, whose purpose is toprovide incorporation into the polymer backbone and Q₄ is as definedpreviously. Q₄ may be incorporated to offset the increased polymerhydrophobicity caused by introduction of the aliphatic hydrocarbonmoieties. Examples of suitable Q₄ moieties are (but not limited to) thealiphatic polyether derivatives of the formula —[(CR₁R₂)_(x)O]_(y)—R₃,wherein R₁, R₂ is H or CH₃, x≧2, y≧1 and R₃ is any suitable terminalgroup including —CH₃, —H, —C₂H₅, —NH₂.

It should be appreciated that when the Q₃ or other charged moiety ispresent in the synthetic polymer, that a suitable counterion will benecessary. Such counterions may or may not be represented in theformulas. Where such counterions are not represented in the formula itshould be understood that such an ion will exist. The specificcounterion is not critical for the invention, such counterion is onlynecessary for providing charge balance. For cationically charged groupsthe most common anions are those of the halides and alkyl sulfates. Foranionically charged groups on the polymer the most common counter ionswill be those of the alkali and alkaline earth metals as well as ammoniaand amine derivatives.

More specifically, the invention resides in a synthetic polymer havingthe following structure:

where:

w≧1;

R₁,R₁′,R₂,R₃=H, C₁₋₄ alkyl;

a, b>0;

c,d≧0 such that c+d>0;

Q₄=a monomer unit or a block or graft copolymer containing a hydrophilicmoiety, which is desirable for making the material into a form suitablefor papermaking. Q₄ may take the form of —Z₂—Q₄—Z₂′— where Z₂, Z₂′ areany bridging radicals, the same or different, whose purpose is toprovide incorporation into the polymer backbone and Q₄ is as definedpreviously. Q₄ may be incorporated to offset the increased polymerhydrophobicity caused by introduction of the aliphatic hydrocarbonmoieties. Examples of suitable Q₄ moieties are (but is not limited to)the aliphatic polyether derivatives of the formula—[(CR₁R₂)_(x)O]_(y)—R₃, wherein R₁, R₂ is H or CH₃, x≧2, y≧1 and R₃ isany suitable terminal group including —CH₃, —H, —C₂H₅, —NH₂;

R₀=any group capable of forming hydrogen or covalent bonds withcellulose. Preferred are —CONH₂, —COOH, COO⁻M⁺, —OH, —CONHCHOHCHO andmixtures of said groups;

A₁=—H, —COOH;

R₄=Z—R₆—Y radical where:

Z=aryl, —CH₂—, —COO—, —CONR′—, —O—, —S—, —OSO₂O—, —CONHCO—,—CONHCHOHCHOO— or any other radical capable of bridging the R₆ group tothe vinyl backbone portion of the molecule. (R′=H, alkyl);

R₆=any linear or branched, saturated or unsaturated, substituted ornon-substituted aliphatic hydrocarbon;

Y=H₁—N⁺R₇R₈R₉, —NR₇R₈, where R₇, R₈, R₉ are same or different and are Hor C₁₋₃₀ linear or branched, saturated or unsaturated aliphatichydrocarbons;

At least one of R₆, R₇, R₈, R₉ must be an aliphatic, linear or branched,substituted or non-substituted, hydrocarbon of chain length 8 or higher;

R₅=Z₂—R₁₀—W;

Z₂=aryl, —CH₂—, —COO—, —CONH—, —O—, —S—, —OSO₂O—, any radical capable ofbridging the R₁₀ group to the vinyl backbone portion of the molecule;

R₁₀=any linear or branched, aliphatic or aromatic hydrocarbon of 2 ormore carbons, preferably —(CH₂CH₂)—, —C(CH₃)₂CH₂CH₂—; and

W=—N⁺R₁₁,R₁₂,R₁₃ where R₁₁, R₁₂, R₁₃ is a C₁₋₄ alkyl group.—[CH₂CR₃R₅]_(c)— may also be the residue formed by co-polymerizationwith dimethyldiallyl ammonium chloride. In this case thecharge-containing residue —[CH₂CR₃R₅]_(c)— will be the form of monomerswith repeat units of structure:

In another aspect, the invention resides in a paper sheet, such as atissue sheet, comprising a synthetic polymer having hydrogen bondingcapability and containing an aliphatic hydrocarbon moiety, said polymerhaving the following structure:

where:

a, b>0;

c,d≧0;

w≧1;

Q₁=a monomer unit or a block or graft copolymer containing a pendantgroup capable of forming hydrogen or covalent bonds with cellulose.Preferred pendant groups for hydrogen bonding are —CONH₂, —COOH,—COO⁻M⁺, —OH and mixtures of said groups. Preferred pendant groups forcovalent bonding are aldehydes and anhydrides. M⁺ can be any suitablecounter ion including Na⁺, K⁺, Ca⁺² and the like;

Q₂=a monomer unit or a block or graft copolymer containing a C₈ orhigher linear or branched, saturated or unsaturated, substituted orunsubstituted aliphatic hydrocarbon moiety. Q₂ may take the form of—Z₁—Q₂—Z₁′— where Z₁, Z₁′ are any bridging radicals, the same ordifferent, whose purpose is to provide incorporation into the polymerbackbone and Q₂ is as defined previously;

Q₃=a monomer unit or a block or graft copolymer containing a chargefunctionality. Such charge functionality is preferably cationic but maybe anionic or amphoteric; and

Q₄=a monomer unit or a block or graft copolymer containing a hydrophilicmoiety, which is desirable for making the material into a form suitablefor papermaking. Q₄ may take the form of —Z₂—Q₄—Z₂′— where Z₂, Z₂′ areany bridging radicals, the same or different, whose purpose is toprovide incorporation into the polymer backbone and Q₄ is as definedpreviously. Q₄ may be incorporated to offset the increased polymerhydrophobicity caused by introduction of the aliphatic hydrocarbonmoieties. Examples of suitable Q₄ moieties are (but is not limited to)the aliphatic polyether derivatives of the formula—[(CR₁R₂)_(x)O]_(y)—R₃, wherein R₁, R₂ is H or CH₃, x≧2, y≧1 and R₃ isany suitable terminal group including —CH₃, —H, —C₂H₅, —NH₂.

More specifically, the invention resides in a paper sheet, such as atissue sheet, comprising a synthetic polymer having hydrogen bondingcapability and containing an aliphatic hydrocarbon moiety, said polymerhaving the following structure:

where:

w≧1;

R₁,R₁′,R₂,R₃=H, C₁₋₄ alkyl;

a, b>0;

c,d>,=0;

Q₄=a monomer unit or a block or graft copolymer containing a hydrophilicmoiety, which is desirable for making the material into a form suitablefor papermaking. Q₄ may take the form of —Z₂—Q₄—Z₂′— where Z₂, Z₂′ areany bridging radicals, the same or different, whose purpose is toprovide incorporation into the polymer backbone and Q₄ is as definedpreviously. Q₄ may be incorporated to offset the increased polymerhydrophobicity caused by introduction of the aliphatic hydrocarbonmoieties. Examples of suitable Q₄ moieties are (but is not limited to)the aliphatic polyether derivatives of the formula—[(CR₁R₂)_(x)O]_(y)—R₃, wherein R₁, R₂ is H or CH₃, x≧2, y≧1 and R₃ isany suitable terminal group including —CH₃, —H, —C₂H₅, —NH₂;

R₀=any group capable of forming hydrogen or covalent bonds withcellulose. Preferred are —CONH₂, —COOH, COO⁻M⁺, —OH, —CONHCHOHCHO, andanhydride including mixtures of said groups;

A₁=H, COOH;

R₄=Z—R₆—Y radical where:

Z=aryl, —CH₂—, —COO—, —CONR′—, —O—, —S—, —OSO₂O—, —CONHCO—,—CONHCHOHCHOO— or any radical capable of bridging the R₆ group to thevinyl backbone portion of the molecule. (R′=—H, alkyl);

R₆=any aliphatic, linear or branched, saturated or unsaturated,substituted or non-substituted hydrocarbon;

Y=—H, —N⁺R₇R₈R₉, —NR₇R₈, where R₇, R₈, R₉ are same or different and areH or C₁₋₃₀ linear or branched, saturated or unsaturated aliphatichydrocarbons;

At least one of R₆, R₇, R₈, R₉ must be an aliphatic, linear or branched,substituted or non-substituted, hydrocarbon of chain length 8 or higher;

R₅=Z₂—R₁₀—W;

Z₂=aryl, —CH₂, —COO—, —CONH—, —O—, —S—, —OSO₂O— or any radical capableof bridging the R₁₀ group to the vinyl backbone portion of the molecule;

R₁₀=any linear or branched, aliphatic or aromatic hydrocarbon of 2 ormore carbons, preferably —(CH₂CH₂)—, —C(CH₃)₂CH₂CH₂—; and

W=—N⁺R₁₁,R₁₂,R₁₃ where R₁₁, R₁₂, R₁₃ is a C₁₋₄ alkyl group.—[CH₂CR₃R₅]_(c)— may also be the residue formed by co-polymerizationwith dimethyldiallyl ammonium chloride. In this case thecharge-containing residue —[CH₂CR₃R₅]_(c)— will be the form of monomerswith repeat units of structure:

In another aspect, the invention resides in a method of making a papersheet, such as a tissue sheet, comprising the steps of: (a) forming anaqueous suspension of papermaking fibers; (b) depositing the aqueoussuspension of papermaking fibers onto a forming fabric to form a web;and (c) dewatering and drying the web to form a paper sheet, wherein asynthetic polymeric additive is added to the aqueous suspension offibers or to the web, said polymeric additive having the followingstructure:

where:

a, b>0;

c,d≧0;

w≧1;

Q₁=a monomer unit or a block or graft copolymer containing a pendantgroup capable of forming hydrogen or covalent bonds with cellulose.Preferred pendant groups for hydrogen bonding are —CONH₂, —COOH,—COO⁻⁺M, —OH and mixtures of said groups. Preferred pendant groups forcovalent bonding are aldehydes and anhydrides. M+ can be any suitablecounter ion including Na⁺, K⁺, Ca⁺² and the like;

Q₂=a monomer unit or a block or graft copolymer containing a C₈ orhigher linear or branched, saturated or unsaturated, substituted orunsubstituted aliphatic hydrocarbon moiety. Q₂ may take the form of—Z₁—Q₂—Z₁′— where Z₁, Z₁′ are any bridging radicals, the same ordifferent, whose purpose is to provide incorporation into the polymerbackbone and Q₂ is as defined previously;

Q₃=a monomer unit or a block or graft copolymer containing a chargefunctionality. Such charge functionality is preferably cationic but maybe anionic or amphoteric; and

Q₄=a monomer unit or a block or graft copolymer containing a hydrophilicmoiety, which is desirable for making the material into a form suitablefor papermaking. Q₄ may take the form of —Z₂—Q₄—Z₂′— where Z₂, Z₂′ areany bridging radicals, the same or different, whose purpose is toprovide incorporation into the polymer backbone and Q₄ is as definedpreviously. Q₄ may be incorporated to offset the increased polymerhydrophobicity caused by introduction of the aliphatic hydrocarbonmoieties. Examples of suitable Q₄ moieties are (but is not limited to)the aliphatic polyether derivatives of the formula—[(CR₁R₂)_(x)O]_(y)—R₃, wherein R₁, R₂ is —H or —CH₃, x≧2, y≧1 and R₃ isany suitable terminal group including —CH₃, —H, —C₂H₅, —NH₂.

More specifically, the invention resides in a method of making a papersheet, such as a tissue sheet, comprising the steps of: (a) forming anaqueous suspension of papermaking fibers; (b) depositing the aqueoussuspension of papermaking fibers onto a forming fabric to form a web;and (c) dewatering and drying the web to form a paper sheet, wherein asynthetic polymeric additive is added to the aqueous suspension offibers or to the web, said polymeric additive having the followingstructure:

where:

w≧1;

R₁,R₁′,R₂, R₃=H, C₁₋₄ alkyl;

a, b>0;

c,d≧0;

Q₄=a monomer unit or a block or graft copolymer containing a hydrophilicmoiety, which is desirable for making the material into a form suitablefor papermaking. Q₄ may take the form of —Z₂—Q₄—Z₂′— where Z₂, Z₂′ areany bridging radicals, the same or different, whose purpose is toprovide incorporation into the polymer backbone and Q₄ is as definedpreviously. Q₄ may be incorporated to offset the increased polymerhydrophobicity caused by introduction of the aliphatic hydrocarbonmoieties. Examples of suitable Q₄ moieties are (but is not limited to)the aliphatic polyether derivatives of the formula—[(CR₁R₂)_(x)O]_(y)—R₃, wherein R₁, R₂ is H or CH₃, x≧2, y≧1 and R₃ isany suitable terminal group including —CH₃, —H, —C₂H₅, —NH₂;

R₀=any group capable of forming hydrogen or covalent bonds withcellulose. Preferred are —CONH₂, COOH, COO⁻, —OH, CONHCHOHCHO, andanhydride including mixtures of said groups;

A₁=—H, —COOH;

R₄=Z—R₆—Y radical where:

Z=aryl, —CH₂—, —COO—, —CONR′—, —O—, —S—, —OSO₂O—, —CONHCO—,—CONHCHOHCHOO— or any radical capable of bridging the R₆ group to thevinyl backbone portion of the molecule. (R′=H, alkyl);

R₆=any aliphatic, linear branched, saturated or unsaturated, substitutedor non-substituted hydrocarbon;

Y=H, —N⁺R₁₁,R₁₂,R₁₃, —NR₇R₈, where R₇, R₈, R₉ are same or different andare H or C₁₋₃₀ linear or branched, saturated or unsaturated aliphatichydrocarbons;

At least one of R₆, R₇, R₈, R₉ must be an aliphatic, linear or branched,substituted or non-substituted, hydrocarbon of chain length 8 or higher;

R₅=Z₂—R₁₀—W;

Z₂=aryl, —CH₂—, —COO—, —CONH—, —O—, —S—, —OSO₂O— or any radical capableof bridging the R₁₀ group to the vinyl backbone portion of the molecule;

R₁₀=any linear or branched, aliphatic or aromatic hydrocarbon of 2 ormore carbons, preferably —(CH₂CH₂)—, —C(CH₃)₂CH₂CH₂—; and

W=—N⁺R₁₁,R₁₂,R₁₃ where R₁₁, R₁₂, R₁₃ is a C₁₋₄ alkyl group.—[CH₂CR₃R₅]_(c)— may also be the residue formed by co-polymerizationwith dimethyldiallyl ammonium chloride. In this case thecharge-containing residue —[CH₂CR₃R₅]_(c)— will be the form of monomerswith repeat units of structure:

The amount of the synthetic polymeric additive added to the fibers orthe tissue web can be from about 0.02 to about 4 weight percent, on adry fiber basis, more specifically from about 0.05 to about 2 weightpercent, and still more specifically from about 0.1 to about 1 weightpercent. The synthetic polymer can be added to the fibers or web at anypoint in the process, but it can be particularly advantageous to add thesynthetic polymer to the fibers while the fibers are suspended in water.

DETAILED DESCRIPTION OF THE INVENTION

To further describe the invention, examples of the synthesis of some ofthe various chemical species are given below.

First with regard to the synthetic polymers, they can be made via freeradical polymerization of vinyl monomers of the form:

R₁R₂C=CR₃R₄

where R₁, R₂, R₃, R₄ may be H, halogen, alkyl, functional alkyl, aryl,functional aryl. For papermaking the polyacrylamides (R₄=—CONH₂),polyvinyl alcohols (R₄=—OH), and polyacrylates (R₄=—COOR′, R′=H, Me) arethe most widely used.

Of the modified vinyl synthetic polymers, polyacrylamides (PAMs) areused as dry strength additives in addition to their widespread use asdrainage and retention aids. They are water-soluble polymers containingprimary amide groups that can form hydrogen bonds with cellulosemolecules in fibers thereby increasing interfiber bonding. They aresynthesized by the free radical polymerization of acrylamide as shown inFigure 1.

(PAMs) per se are nonionic materials and have very little attraction topapermaking fibers. Therefore it is necessary to incorporate chargedgroups into the polymer structure to make it useful for papermaking.Both anionic and cationic polyacrylamides are known in the art.

Anionic polyacrylamides can be produced by (1) the copolymerization ofacrylamide with acrylic acid or the (2) hydrolysis of some of the amidegroups on the polyacrylamide chain. The resultant polymer will contain amixture of acrylamide and acrylic acid groups. Anionic polyacrylamideswere first produced in the 1950's via copolymerization of acrylamidewith acrylic acid. The acrylic acid groups introduce an ionizablecarboxyl group on the polymer backbone. Ionization of these carboxylgroups is highly pH dependent, where above pH 7 essentially 100% of thecarboxyl groups are ionized. Since anionic polyacrylamides arenegatively charged they are not directly attracted to the like-chargedcellulose papermaking fibers. A cationic substance such as alum must beused in conjunction with them to promote their retention.

To avoid the need for a cationic promoter, another approach is toincorporate cationic groups directly into the polymer backbone. Havingbeen commercially produced since the late 1960's, these cationicallycharged polyacrylamides are the most common form of dry strength PAM's.Cationic polyacrylamides are produced by copolymerization of acrylamidewith cationic monomers or by modification of some of the amide groups.Typical cationic monomers include: (1) methacryloyloxyethyl trimethylammonium methosulfate (METAMS); (2) dimethyldiallyl ammonium chloride(DMDAAC); (3) 3-acryloamido-3-methyl butyl trimethyl ammonium chloride(AMBTAC); (4) trimethylamino methacrylate; and (5) vinyl benzyltrimethyl ammonium chloride (VBTAC). A typical reaction forco-polymerization with METAMS is illustrated in Figure 2.

Production of cationic polyacrylamides by the modification of the amidegroups of PAMs is most often accomplished via the Mannich reaction asillustrated in Figure 3. Generally cationic polyacrylamides synthesizedin this manner will contain from about 5 to about 70 mole percentcationic groups.

Generally dry strength PAMs are supplied as ready to use aqueoussolutions or as water-soluble powders which must be dissolved prior touse. They may be added to thin or thick stock at a point of good mixingfor best results. Addition rates of 0.1% to 0.5% of dry fiber typicallygive best results. High addition rates may cause over-cationization ofthe furnish and reduce the effectiveness of other additives.

When used as dry strength additives usually around 10 mole % of themonomers will contain charged groups. Unlike the anionic PAMs, cationicPAMs can be effectively charged across the entire pH range. Typicalmolecular weights (Mw) for cationic PAM dry strength aids are in therange of 100,000 to 500,000. The molecular weight is important so as tobe low enough to not bridge between particles and cause flocculation,and yet high enough to retard migration of the polymer into the pores ofthe fibers. Such migration would cause a reduction in dry strengthactivity.

When used as retention aids a broader range of molecular weights andcharge densities may be employed. Key characteristics of polyacrylamideretention aids include the molecular weight, the type of charge, thecharge density and the delivery form. For the average molecular weight,the range can be: low (1,000-100,000); medium (100,000-1,000,000); high(1,000,000-5,000,000); very high (>5,000,000). The charge type can benonionic, cationic, anionic or amphoteric. The charge density can be:low (1-10%); medium (10-40%); high (40-80%); or very high (80-100%). Thedelivery form can be an emulsion, an aqueous solution or a dry solid.

High molecular weight/low charge density flocculants are used most oftenfor retention of fine particles in high shear and turbulenceenvironments. Low Mw, high charge density products are used for theircharge modifying capabilities and for retention in low shearenvironments.

There are several envisioned pathways in which synthetic polymerscontaining hydrogen bonding groups and aliphatic hydrocarbons can becombined onto a single molecule for purposes of this invention. Theseinclude, but are not limited to: (1) block co-polymerization and/orgrafting ; (2) direct monomer incorporation ; and (3) derivatization offunctional groups on the polymer backbone. Each of these methods isdescribed below. Since these materials maintain their bonding and/orcharge characteristics they would be expected to maintain their drystrength and or retention capabilities as well as provide for materialswith enhanced tactile properties due to introduction of the aliphatichydrocarbon moieties.

The molar and weight ratios of the various functional groups on thepolymer will largely depend on the specific application of the materialand is not a critical aspect of the invention. However, the portion ofthe synthetic polymer [Q₁] capable of forming hydrogen, covalent andionic bonds can constitute from about 10 to about 90 weight percent ofthe total polymer, more specifically from about 20 to about 80 weightpercent of the total polymer and still more specifically from about 30to about 70 weight percent of the total polymer. The aliphatichydrocarbon portion [Q₂] of the synthetic polymer can constitute fromabout 10 to about 90 weight percent of the synthetic polymer, morespecifically from about 20 to about 80 weight percent of the syntheticpolymer and still more specifically from about 30 to about 70 weightpercent of the synthetic polymer. The charge containing portion [Q₃] ofthe synthetic polymer can be comprised of monomer units constitutingfrom 0 to about 80 mole percent of the total monomer units in thesynthetic polymer, more specifically from 0 to about 30 mole percent andstill more specifically from about 5 to about 15 mole percent. The [Q₄]functionality will be comprised of monomer units constituting from 0 toabout 80 mole percent of the total monomer units in the syntheticpolymer, more specifically from 0 to about 40 mole percent and stillmore specifically from 0 to about 20 mole percent.

Likewise the molecular weight of the synthetic polymers of the presentinvention will largely depend on the specific application of thematerial and is not overly critical to the invention. The weight averagemolecular weight range can be from about 1,000 to about 5,000,000, morespecifically from about 10,000 to about 2,000,000 and still morespecifically from about 20,000 to about 1,000,000. Where these polymersare added for dry strength it is important that the molecular weight ofthe polymer be low enough so as to not bridge between particles andcause flocculation, and yet high enough so as to retard migration of thepolymer into the pores of the fibers. These materials can have weightaverage molecular weights in the range of from about 5,000 to about1,000,000, more specifically from about 10,000 to about 1,000,000 andstill more specifically from about 20,000 to about 600,000.

Block Copolymerization and/or Grafting

In this aspect of the invention one or more of the [Q]_(i) elements ofthe polymer exists as a block or graft copolymer on the vinyl backbone.For example, if the aliphatic hydrocarbon portion of the modified vinylpolymer was incorporated in such a manner, the aliphatic hydrocarbonportion would exist as a block copolymer of polyethylene, polypropylene,isobutylene, polytetraflouroethylene, or any other linear or branched,saturated or unsaturated, substituted or non-substituted hydrocarbon,such co-polymer incorporated either as block or graft onto the vinylbackbone. Generally the aliphatic hydrocarbon blocks would be built as aresult of the free radical polymerization of the correspondingethylenically unsaturated monomers including, ethylene, propylene,perflouroethylene, isobutylene and the like including mixtures of saidmonomers. These synthetic polymers are distinguished from those of thedirect monomer incorporation in that the aliphatic hydrocarbon portionof the molecule would be incorporated linearly within the polymer chainrather than in a pendant fashion. Although the above example and theexample in Figure 4 are specific to the aliphatic hydrocarbon moietyincorporated via this approach it should be appreciated that any of thesynthetic polymer elements or combination of the synthetic polymerelements Q₁, Q₂, Q₃, Q₄ could be incorporated via this approach. Notethat where a polyacrylamide is employed that these polymers maintainpendant amide functionality and are therefore capable of beingglyoxylated to form materials possessing temporary wet strength. Ageneral example of preparing such a material is shown in Figure 4.

where:

R₁, R₃,R₁′=H, C₁₋₄ alkyl

g, h, x≧1

x*y=g

b*y=h

a, b>0

c,d≧0

R₀=any group capable of forming hydrogen or covalent bonds withcellulose. Preferred are —CONH₂, COOH, COO⁻, —OH, CONHCHOHCHO, andanhydride including mixtures of said groups;

A₁=H, COOH

M₁=an unsaturated vinyl monomer unit capable of being polymerized into apolymer containing a C₈ or higher linear or branched, saturated orunsaturated, substituted or unsubstituted aliphatic hydrocarbon moiety.Alternatively M₁ could be an oligomer or polymer of such an unsaturatedvinyl monomer.

Q₂=a block copolymer which is or contains a C₈ or higher linear orbranched, saturated or unsaturated, substituted or unsubstitutedaliphatic hydrocarbon moiety.

Q₄=a monomer unit or a block or graft copolymer containing a hydrophilicmoiety, which is desirable for making the material into a form suitablefor papermaking. Q₄ may take the form of —Z₂—Q₄—Z₂′— where Z₂, Z₂′ areany bridging radicals, the same or different, whose purpose is toprovide incorporation into the polymer backbone and Q₄ is as definedpreviously. Q₄ may be incorporated to offset the increased polymerhydrophobicity caused by introduction of the aliphatic hydrocarbonmoieties. Examples of suitable Q₄ moieties are (but is not limited to)the aliphatic polyether derivatives of the formula—[(CR₁R₂)_(x)O]_(y)—R₃, wherein R₁, R₂ is H or CH₃, x≧2, y≧1 and R₃ isany suitable terminal group including —CH₃, —H, —C₂H₅, —NH₂

R₅=Z₂—R₁₀—W

Z₂=Aryl, CH₂, COO—, CONH—, —O—, —S—, —OSO₂O—, any radical capable ofbridging the R₁₀ group to the vinyl backbone portion of the molecule.

R₁₀=any linear or branched, aliphatic or aromatic hydrocarbon of 2 ormore carbons, preferably —(CH₂CH₂)—, —C(CH₃)₂CH₂CH₂—

W=—N⁺R₁₁,R₁₂,R₁₃, NR₁₁R₁₂, where R₁₁, R₁₂, R₁₃ is a C₁₋₄ alkyl group.

R₅ may also be the residue formed by co-polymerization withdimethyldiallyl ammonium chloride. In this case the residue will be theform of monomers with repeat units of structure:

Direct Monomer Incorporation

Incorporation of the aliphatic moieties can be accomplished viacopolymerization with vinyl type monomers containing aliphatic groups.Almost any vinyl type monomer containing a pendant aliphatic hydrocarboncan be co-polymerized with acrylamide or a similar vinyl monomercontaining a pendant hydrogen-bonding moiety to be incorporated into thepolymer backbone. Generically the synthesis can be described in Figure5.

where:

R₁, R₁′, R₁″, R₁′″, R₁″″=H, C₁₋₄ alkyl;

a, b≧1;

c,d≧0;

w≧1;

r,s≧1;

t,u≧0;

a*w=r;

b*w=s;

c*w=t;

d*w=u;

R₀=any group capable of forming hydrogen or covalent bonds withcellulose. Preferred are —CONH₂, COOH, COO⁻, —OH, CONHCHOHCHO, andanhydride including mixtures of said groups;

A₁=H, COOH;

R₄=Z—R₆—Y radical where:

Z=Aryl, CH₂, COO—, CONH—, —O—, —S—,—OSO₂O—, —CONHCO—, CONHCHOHCHOO—, anyradical capable of bridging the R₆ group to the vinyl backbone portionof the molecule;

Y=H, —N+R₇R₈R₉, —NR₇R₈, where R₇, R₈, R₉ are same or different and are Hor C₁₋₃₀ aliphatic hydrocarbons;

R₅=any aliphatic, linear or branched, saturated or unsaturated,substituted or non-substituted hydrocarbon;

R₁₄=a moiety necessary for making the material into a form suitable forpapermaking. R₁₄ may take the form of —Z₁—R₁₄ where Z₁ is any bridgingradical whose purpose is to provide incorporation into the polymerbackbone and R₁₄ is as defined previously. R₁₄ may be incorporated tooffset the increased polymer hydrophobicity caused by introduction ofthe aliphatic hydrocarbon moieties. Examples of suitable R₁₄ moietiesare (but is not limited to) the aliphatic polyether derivatives of theformula —[(CR₁R₂)_(x)O]_(y)—R₁₅, wherein R₁, R₂ is H or CH₃, x≧2, y≧1and R₁₅ is any suitable terminal group including —CH₃, —H, —C₂H₅, —NH₂and the like; and

At least one of R₆, R₇, R₈, R₉ must be a C₈ or higher linear orbranched, saturated or unsaturated, substituted or non-substituted,aliphatic hydrocarbon.

More specifically, R₅=Z₂—R₁₀—W, where:

Z₂=Aryl, CH₂, COO—, CONH—, —O—, —S—, —OSO₂O—, any radical capable ofbridging the R10 group to the vinyl backbone portion of the molecule;

R₁₀=any linear or branched, aliphatic or aromatic hydrocarbon of 2 ormore carbons, preferably —(CH₂CH₂)—, —C(CH₃)₂CH₂CH₂—; and

W=—N⁺R₁₁,R₁₂,R₁₃ where R₁₁, R₁₂, R₁₃ is a C₁₋₄ alkyl group.

R₅ can also be the residue formed by co-polymerization withdimethyldiallyl ammonium chloride. In this case the residue will be theform of monomers with repeat units of structure:

A specific example of the synthesis is shown in Figure 6.

Long chain acrylates, including octadecyl acrylate, octadecylmethacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecylacrylate, dodecyl methacrylate, tridecyl acrylate, tridecylmethacrylate, lauryl acrylate, lauryl methacrylate and the likeincluding mixtures of said monomers are known commercially availablematerials and are all suitable for incorporation of the aliphatichydrocarbon moiety.

Also known are various vinyl ethers dodecyl vinyl ether, tridecyl vinylether, tetradecyl vinyl ether, pentadecyl vinyl ether, hexadecyl vinylether, and esters such as those derived from aliphatic alcohols andα,β-ethylenic unsaturated carboxylic acids including vinyl neodecanoate,vinyl neononaoate, vinyl stearate, vinyl 2-ethylhexanoate, vinyldodecanoate, vinyl tetradecanoate, vinyl hexadecanoate and the likeincluding mixtures of said monomers, all of which are suitable forincorporation of the aliphatic hydrocarbon moiety.

Also suitable for incorporation of the aliphatic hydrocarbon moiety, butless preferred, are the α-unsaturated and β-unsaturated olefinichydrocarbon derivatives such as 1-octadecene, 1-dodecene, 1-hexadecene,1-heptadecene, 1-tridecene, 1-undecene, 1-decene, 1-pentadecene,1-tetradecene, 2-octadecene, 2-dodecene, 2-hexadecene, 2-heptadecene,2-tridecene, 2-undecene, 2-decene, 2-pentadecene, 2-tetradecene, and thelike including mixtures of said monomers. They can be incorporated intoany vinyl type polymer such as polyacrylamide, polyvinyl alcohol,polyacrylic acid, polyvinyl acetate, polymethacrylic acid, polyitaconic,poly(maleic acid), poly(maleic anhydride), polyacrylonitrile and thelike. For the purposes of papermaking, the polyacrylamides, polyvinylalcohols and polyacrylic acids are most preferred. They would beincorporated directly into the polymer via copolymerization with theassociated ethylenically unsaturated monomers including acrylamide,vinyl alcohol, acrylic acid, methacrylic acid, itaconic acid, maleicacid, acrylonitrile and the like including mixtures of said monomersduring the polymerization process as described below. The descriptionshown is specific for a polyacrylamide but is applicable to any vinyltype polymer. When incorporated in such a manner the long chainaliphatic groups are arranged on the polymer in a pendant fashion.

Suitable monomers for incorporating a charge functionality into thepolymer include, but are not limited to methacryloyloxyethyl trimethylammonium methosulfate (METAMS); dimethyldiallyl ammonium chloride(DMDAAC); 3-acryloamido-3-methyl butyl trimethyl ammonium chloride(AMBTAC); trimethylamino methacrylate; vinyl benzyl trimethyl ammoniumchloride (VBTAC), 3-allyloxy-2-hydroxy-1propane sulfonic acid sodiumsalt and the like including mixtures of said monomers.

Suitable monomers for incorporating a functionality for making thepolymer into a form suitable for papermaking includes but is not limitedto: ethylene glycol acrylate, ethylene glycol methacrylate, diethyleneglycol acrylate, diethylene glycol methacrylate, 2-allyloxyethanol,3-allyloxy-1,2-propanediol, poly(ethylene glycol) acrylate,poly(ethylene glycol) methacrylate, poly(ethylene glycol) diacrylate,poly(ethylene glycol) dimethacrylate, poly(ethylene glycol) methyl etheracrylate, poly(ethylene glycol) methyl ether methacrylate, poly(ethyleneglycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ethermethacrylate, poly(ethylene glycol) divinyl ether, poly(ethylene glycol)phenyl ether acrylate, poly(propylene glycol) acrylate, poly(propyleneglycol) methacrylate, poly(propylene glycol)diacrylate, poly(propyleneglycol) dimethaerylate, poly(propylene glycol) methyl ether acrylate,poly(propylene glycol) methyl ether methacrylate, poly(propylene glycol)ethyl ether acrylate, poly(propylene glycol) ethyl ether methacrylate,poly(propylene glycol) phenyl ether acrylate and the like includingmixtures of said monomers.

Note that where acrylamide is employed that the resultant polymerscontain pendant amide functionality that is capable of being glyoxylatedto form materials possessing temporary wet strength as shown in Figures7 and 8.

Where:

w≧1;

R₁,R₁′,R₂, R₃=H, C₁₋₄ alkyl;

a, b>0;

c,d≧0;

R₄=Z—R₆—Y radical where:

Z=Aryl, CH₂, COO—, CONR′—, —O—, —S—, —OSO₂O—, —CONHCO—, —CONHCHOHCHOO—,any radical capable of bridging the R₆ group to the vinyl backboneportion of the molecule. (R′=H, alkyl);

R₆=any aliphatic, linear or branched, saturated or unsaturated,substituted or non-substituted hydrocarbon;

Y=H, —N+R₇R₈R₉, —NR₇R₈, where R₇, R₈, R₉ are same or different and are Hor C₁₋₃₀ linear or branched, saturated or unsaturated aliphatichydrocarbons;

At least one of R₆, R₇, R₈, R₉ must be an aliphatic, linear or branched,substituted or non-substituted, hydrocarbon of chain length 8 or higher;

R₅=Z₂—R₁₀—X;

Z₂=Aryl, CH₂, COO—, CONH—, —O—, —S—, —OSO₂O—, any radical capable ofbridging the R₁₀ group to the vinyl backbone portion of the molecule;

R₁₀=any linear or branched, aliphatic or aromatic hydrocarbon of 2 ormore carbons, preferably —(CH₂CH₂)—, —C(CH₃)₂CH₂CH₂—; and

X=—N+R₁₁,R₁₂,R₁₃ where R₁₁, R₁₂, R₁₃ is a C₁₋₄ alkyl group.

R₅ may also be the residue formed by co-polymerization withdimethyldiallyl ammonium chloride. In this case the residue will be theform of monomers with repeat units of structure:

Derivatization of Functional Groups on the Polymer Backbone

The third approach to synthesis of materials of this invention is tomodify the functional groups on the polymer backbone. The vinyl typepolymers such as polyacrylamides, modified polyacrylamides, polyacrylicacids, polyvinyl alcohols, polymaleic acid, polymaleic anhydride andpolyacrylonitriles contain functional groups which may be furtherderivatized to produce materials of the structure of Figure 4. Thepolymer functional groups which may be reacted upon include but are notlimited to: amide, carboxyl, hydroxyl, anhydride, cyano, thiol andaldehyde (from glyoxylation or similar reaction). In general thestarting polymer will be one of that shown in Figure 9.

where:

R₁=H, C,₁₋₄ alkyl;

a, b≧1;

c,d≧0;

Q₁=a monomer unit or a block or graft copolymer containing a pendantgroup capable of forming hydrogen or covalent bonds with cellulose.Preferred pendant groups for hydrogen bonding are —CONH₂, —COO⁻⁺M, —OHand mixtures of said groups. Preferred pendant groups for covalentbonding are aldehydes and anhydrides. M+ can be any suitable counter ionincluding Na⁺, K⁺, Ca⁺² and the like;

Q₃=a monomer unit or a block or graft copolymer containing a chargefunctionality. Such charge functionality is preferably cationic but maybe anionic or amphoteric;

Z₄=-CONHCHOHCHO, —CHO, —CONH₂, —COOH, —CN, —OH, —SH, —NH₂, —R′OH,—R′CHO, —R′CONH₂, —R′COOH, —R′CN, —R′OH, —R′SH, —R′NH₂ or any otherfunctional group capable of being reacted upon in a manner so as toincorporate a C₈ or higher linear or branched, saturated or unsaturated,substituted or unsubstituted aliphatic hydrocarbon into the polymer andR′ can be any bridging radical, organic or inorganic whose purpose is toattach the functional group to the polymer; and

Q₄=a monomer unit or a block or graft copolymer containing a hydrophilicmoiety, which is desirable for making the material into a form suitablefor papermaking. Q₄ may take the form of —Z₂—Q₄—Z₂′— where Z₂, Z₂′ areany bridging radicals, the same or different, whose purpose is toprovide incorporation into the polymer backbone and Q₄ is as definedpreviously. Q₄ may be incorporated to offset the increased polymerhydrophobicity caused by introduction of the aliphatic hydrocarbonmoieties. Examples of suitable Q₄ moieties are (but is not limited to)the aliphatic polyether derivatives of the formula—[(CR₁R₂)_(x)O]_(y)—R₃, wherein R₁, R₂ is H or CH₃, x≧2, y≧2 and R₃ isany suitable terminal group including —CH₃, —H, —C₂H₅, —NH₂.

Such structures as those shown in Figure 9 are amenable to reaction witha large variety of reagents as a means of incorporating aliphaticresidues into the polymer. The general scheme for such syntheses isshown in Figure 10.

where:

R₁=H, C₁₋₄alkyl;

a, b≧1;

c,d≧0;

Q₁=a monomer unit or a block or graft copolymer containing a pendantgroup capable of forming hydrogen or covalent bonds with cellulose.Preferred pendant groups for hydrogen bonding are —CONH₂, —COO⁻⁺M, —OHand mixtures of said groups. Preferred pendant groups for covalentbonding are aldehydes and anhydrides. M+ can be any suitable counter ionincluding Na⁺, K⁺, Ca⁺² and the like;

Q₃=a monomer unit or a block or graft copolymer containing a chargefunctionality. Such charge functionality is preferably cationic but maybe anionic or amphoteric;

Z₄=-CONHCHOHCHO, —CHO, —CONH₂, —COOH, —CN, —OH, —SH, —NH₂, —R′OH,—R′CHO, —R′CONH₂, —R′COOH, —R′CN, —R′OH, —R′SH, —R′NH₂ or any otherfunctional group capable of being reacted upon in a manner so as toincorporate a C₈ or higher linear or branched, saturated or unsaturated,substituted or unsubstituted aliphatic hydrocarbon into the polymer andR′ can be any bridging radical, organic or inorganic whose purpose is toattach the functional group to the polymer; and

Q₄=a monomer unit or a block or graft copolymer containing a hydrophilicmoiety, which is desirable for making the material into a form suitablefor papermaking. Q₄ may take the form of —Z₂—Q₄—Z₂′— where Z₂, Z₂′ areany bridging radicals, the same or different, whose purpose is toprovide incorporation into the polymer backbone and Q₄ is as definedpreviously. Q₄ may be incorporated to offset the increased polymerhydrophobicity caused by introduction of the aliphatic hydrocarbonmoieties. Examples of suitable Q₄ moieties are (but is not limited to)the aliphatic polyether derivatives of the formula—[(CR₁R₂)_(x)O]_(y)—R₃, wherein R₁, R₂ is H or CH₃, x≧2, y≧2 and R₃ isany suitable terminal group including —CH₃, —H, —C₂H₅, —NH₂.

Z₅=HOOC—, ClOC—, HO—, HS—, —COOOC—, H₂N—, HCO—, ClSO₂O—, XOC—(X=halo),ClCOO—, or any other functional group capable of reaction with a Z₄ typefunctional group so as to attach the —R₆—Y residue onto the polymer;

R₆=any aliphatic, linear or branched, saturated or unsaturated,substituted or non-substituted hydrocarbon;

Y=H, —N⁺R₇R₈R₉, —NR₇R₈, where R₇, R₈, R₉ are same or different and are Hor C₁₋₃₀ linear or branched, saturated or unsaturated aliphatichydrocarbons; and where at least one of R₆, R₇, R₈, R₉ must be a C₈ orhigher linear or branched, substituted or non-substituted, aliphatichydrocarbon.

Some specific examples of such reactions are given in Figures 11 and 12.

It will be appreciated that the foregoing examples, given for purposesof illustration, are not to be construed as limiting the scope of thisinvention, which is defined by the following claims and all equivalentsthereto.

We claim:
 1. A synthetic polymer containing one or more aliphatichydrocarbon moieties, said synthetic polymer having the followingstructure:

where: a, b, d>0; c≧0; w≧1; Q₁=a monomer unit or a block or graftcopolymer containing a pendant group capable of forming hydrogen orcovalent bonds with cellulose; Q₂=a monomer unit or a block or graftcopolymer containing a C₈ or higher linear or branched, saturated orunsaturated, substituted or unsubstituted aliphatic hydrocarbon moiety;Q₃=a monomer unit or a block or graft copolymer containing a chargefunctionality; and Q₄=a monomer unit or a block or graft copolymercontaining a hydrophilic moiety, which is desirable for making thematerial into a form suitable for papermaking.
 2. The polymer of claim 1wherein the pendant group on Q₁ capable of forming hydrogen or covalentbonds is selected from the group consisting of —CONH₂, —COOH, —COO⁻M⁺,—OH, —CONHCHOHCHO and mixtures thereof, wherein M⁺ is a counter ion. 3.The polymer of claim 1 wherein Q₂ is of the form —Z₁—Q₂—Z₁′— where Z₁,Z₁′ are bridging radicals, which can be the same or different.
 4. Thepolymer of claim 1 wherein Q₄ is of the form —Z₂—Q₄—Z₂′— where Z₂, Z₂′are bridging radicals, which can be the same or different.
 5. Thepolymer of claim 1 wherein Q₄ is a radical of the form —CHR₁CR₃₀ R₁′—wherein R₃₀ is an aliphatic polyether derivative of the formula—[(CR₂R₂)_(x)O]_(y)—R₃ where: R₁, R₁′ is —H, C₁₋₄ alkyl; R₂, R₂′ is —Hor —CH₃; x≧2; y≧2; and R₃ is a terminal group selected from the groupconsisting of —CH₃, —H, —C₂H₅, and —NH₂.
 6. The polymer of claim 1wherein Q₃ is


7. The polymer of claim 1 wherein Q₃ is a radical of the form—CHR₁CR₂₀R₁′— wherein R₂₀=a pendant group of the form Z₁—R₁₀—W, where Z₁is a bridging radical bonding the R₁₀ group to the polymer; R₁ and R₁′are —H or a C₁₋₄ alkyl group; R₁₀=any linear or branched, aliphatic oraromatic hydrocarbon of 2 or more carbons; and W=—N+R₁₁,R₁₂,R₁₃ whereR₁₁, R₁₂, R₁₃ is a C₁₋₄ alkyl group.
 8. The polymer of claim 7 whereinZ₁ is selected from the group consisting of aryl, —CH₂—, —COO—, —CONH—,—O—, —S—, and —OSO₂O—.
 9. The polymer of claim 7 wherein R₁₀ is—(CH₂CH₂)— or —C(CH₃)₂CH₂CH₂—.
 10. The polymer of claim 1 wherein “c” is0.
 11. The polymer of claim 1 wherein the pendant group on Q₁ capable offorming hydrogen bonds is —CONH₂.
 12. The polymer of claim 1 wherein thependant group on Q₁ capable of forming covalent bonds is —CONHCHOHCHO.13. The polymer of claim 1 wherein Q₁ has —CONH₂ and —CONHCHOHCHOpendant groups.
 14. A synthetic polymer having hydrogen bondingcapability and containing one or more aliphatic hydrocarbon moieties,said polymer having the following structure:

where: w≧1; R₁,R₁′,R₂, R₃=H or C₁₋₄alkyl; a, b, d>0; c≧0; R₀=a groupcapable of forming hydrogen or covalent bonds with cellulose; Q₄=amonomer unit or a block or graft copolymer containing a hydrophilicmoiety; A₁=—H, —COOH; R₄=a Z₁—R₆—Y radical, where: Z₁=any radicalcapable of bonding the R₆ group to the polymer; R₆=any linear orbranched, saturated or unsaturated, substituted or non-substitutedaliphatic hydrocarbon; Y=—H, —N⁺R₇R₈R₉, or —NR₇R₈, where R₇, R₈, R₉ aresame or different and are H or C₁₋₃₀ linear or branched, saturated orunsaturated aliphatic hydrocarbons and where: at least one of R₆, R₇,R₈, R₉ must be a linear or branched, substituted or non-substituted,aliphatic hydrocarbon having a carbon chain length of 8 or higher;R₅=Z₁—R₁₀—W, where: Z₁=any radical capable of bonding the R₁₀ group tothe polymer; R₁₀=any linear or branched, aliphatic or aromatichydrocarbon of 2 or more carbons; and W=—N⁺R₁₁,R₁₂,R₁₃, where R₁₁, R₁₂,R₁₃ are C₁₋₄ alkyl groups.
 15. The polymer of claim 14 wherein R₀ isselected from the group consisting of —CONH₂, —COOH, —COO⁻M⁺, —OH,—CONHCHOHCHO, and mixtures thereof, wherein M⁺ is a counter ion.
 16. Thepolymer of claim 14 wherein Q₄ is of the form —Z₂—Q₄—Z₂′— where Z₂, Z₂′are bridging radicals, which can be the same or different.
 17. Thepolymer of claim 14 wherein Z₁ is selected from the group consisting ofaryl, —CH₂—, —COO—, —CONR′—, —O—, —S—, —OSO₂O—, —CONHCO—, and—CONHCHOHCHOO—, and where R′ is H or C₁₋₄ alkyl.
 18. The polymer ofclaim 14 wherein Z₁ is selected from the group consisting of aryl,—CH₂—, —COO—, —CONH—, —O—, —S—, and —OSO₂O—.
 19. The polymer of claim 14wherein R₁₀ is —(CH₂CH₂)— or —C(CH₃)₂CH₂CH₂—.
 20. The polymer of claim14 wherein A₁ is —H and R₀ is —CONH₂.
 21. The polymer of claim 14wherein A₁ is —H and R₀ is —CONHCHOHCHO.
 22. The polymer of claim 14wherein R₀ consists of both —CONH₂ and —CONHCHOHCHO groups.
 23. Asynthetic polymer having hydrogen bonding capability and containing oneor more aliphatic hydrocarbon moieties, said polymer having thefollowing structure:

where: w≧1; R₁,R₁′,R₂,R₃=H or C₁₋₄ alkyl; a, b>0; c,d≧0 such that c+d>0;R₀=a group capable of forming hydrogen or covalent bonds with cellulose;Q₄=a monomer unit or a block or graft copolymer containing a hydrophilicmoiety; A₁=—H, —COOH; R₄=a Z₁—R₆—Y radical, where: Z₁=any radicalcapable of bonding the R₆ group to the polymer; R₆=any linear orbranched, saturated or unsaturated, substituted or non-substitutedaliphatic hydrocarbon; Y=—H, —N⁺R₇R₈R₉, or —NR₇R₈, where R₇, R₈, R₉ aresame or different and are H or C₁₋₃₀ linear or branched, saturated orunsaturated aliphatic hydrocarbons and where: at least one of R₆, R₇,R₈, R₉ must be a linear or branched, substituted or non-substituted,aliphatic hydrocarbon having a carbon chain length of 8 or higher.
 24. Asynthetic polymer containing one or more aliphatic hydrocarbon moieties,said synthetic polymer having the following structure:

where: a, b>0; c, d≧0 such that c+d>0; w≧1; Q₁=a monomer unit or a blockor graft copolymer containing a pendant group capable of forminghydrogen or covalent bonds with cellulose; Q₂=a monomer unit or a blockor graft copolymer containing a C₈ or higher linear or branched,saturated or unsaturated, substituted or unsubstituted aliphatichydrocarbon moiety; Q₃=a monomer unit or a block or graft copolymercontaining an anionic or amphoteric charge functionality; and Q₄=amonomer unit or a block or graft copolymer containing a hydrophilicmoiety, which is desirable for making the material into a form suitablefor papermaking.
 25. The synthetic polymer of claim 24 wherein thependant group on Q₁ capable of forming hydrogen or covalent bonds isselected from the group consisting of —CONH₂, —COOH, —COO⁻M⁺, —OH,—CONHCHOHCHO and mixtures thereof, wherein M⁺ is a counter ion.
 26. Thesynthetic polymer of claim 24 wherein Q₂ is of the form —Z₁—Q₂—Z₁′—where Z₁, Z₁′ are bridging radicals, which can be the same or different.27. The synthetic polymer of claim 24 wherein Q₄ is of the form—Z₂—Q₄—Z₂′— where Z₂, Z₂′ are bridging radicals, which can be the sameor different.
 28. The synthetic polymer of claim 24 wherein Q₄ is aradical of the form —CHR₁CR₃₀R₁′— wherein R₃₀ is an aliphatic polyetherderivative of the formula —[(CR₂R₂)_(x)O]_(y)—R₃ where: R₁, R₁′ is —H,C₁₋₄ alkyl; R₂, R₂′ is —H or —CH₃; x≧2; y≧2; and R₃ is a terminal groupselected from the group consisting of —CH₃, —H, —C₂H₅, and —NH₂.
 29. Thesynthetic polymer of claim 24 wherein “d” is
 0. 30. The syntheticpolymer of claim 24 wherein the pendant group on Q₁ capable of forminghydrogen bonds is —CONH₂.
 31. The synthetic polymer of claim 24 whereinthe pendant group on Q₁ capable of forming covalent bonds is—CONHCHOHCHO.
 32. The synthetic polymer of claim 24 wherein Q₁ has—CONH₂ and —CONHCHOHCHO pendant groups.
 33. A synthetic polymercontaining one or more aliphatic hydrocarbon moieties, said syntheticpolymer having the following structure:

where: a, b>0; c,d>0 such that c+d>0; w≧1; Q₁=a monomer unit or a blockor graft copolymer containing one or more pendant —CONHCHOHCHO groups;Q₂=a monomer unit or a block or graft copolymer containing a C₈ orhigher linear or branched, saturated or unsaturated, substituted orunsubstituted aliphatic hydrocarbon moiety; Q₃=a monomer unit or a blockor graft copolymer containing a charge functionality; and Q₄=a monomerunit or a block or graft copolymer containing a hydrophilic moiety,which is desirable for making the material into a form suitable forpapermaking.
 34. The synthetic polymer of claim 33 wherein Q₁ furtherhas one or more pendant —CONH₂ groups.
 35. A synthetic polymercontaining one or more aliphatic hydrocarbon moieties, said syntheticpolymer having the following structure:

where: a, b>0; c,d≧0 such that c+d>0; w≧1; Q₁=a block or graft copolymercontaining a pendant group capable of forming hydrogen or covalent bondswith cellulose; Q₂=a monomer unit containing a C₈ or higher linear orbranched, saturated or unsaturated, substituted or unsubstitutedaliphatic hydrocarbon moiety; Q₃=a monomer unit containing a chargefunctionality; and Q₄=a monomer unit or a block or graft copolymercontaining a hydrophilic moiety, which is desirable for making thematerial into a form suitable for papermaking.
 36. The synthetic polymerof claim 35 wherein pendant groups on Q₁ capable of forming hydrogen orcovalent bonds are selected from the group consisting of —CONH₂, —COOH,—COO⁻M⁺, —OH, —CONHCHOHCHO and mixtures thereof, wherein M⁺ is a counterion.
 37. The synthetic polymer of claim 35 wherein Q₄ is a radical ofthe form —CHR₁CR₃₀R₁′— wherein R₃₀ is an aliphatic polyether derivativeof the formula —[(CR₂R₂)_(x)O]_(y)—R₃ where: R₁, R₁′ is —H, C₁₋₄ alkyl;R₂, R₂′ is —H or —CH₃; x≧2; y≧2; and R₃ is a terminal group selectedfrom the group consisting of —CH₃, —H, —C₂H₅, and —NH₂.
 38. Thesynthetic polymer of claim 35 wherein Q₃ is


39. The synthetic polymer of claim 35 wherein Q₃ is a radical of theform —CHR₁CR₂₀R₁′— wherein R₂₀=a pendant group of the form Z₁—R₁₀—W,where Z₁ is a radical bonding the R₁₀ group to the polymer; R₁ and R₁′are —H or a C₁₋₄ alkyl group; R₁₀=any linear or branched, aliphatic oraromatic hydrocarbon of 2 or more carbons; and W=—N+R₁₁,R₁₂,R₁₃ whereR₁₁, R₁₂, R₁₃ is a C₁₋₄ alkyl group.
 40. The synthetic polymer of claim39 wherein Z₁ is selected from the group consisting of aryl, —CH₂—,—COO—, —CONH—, —O—, —S—, and —OSO₂O—.
 41. The synthetic polymer of claim39 wherein R₁₀ is —(CH₂CH₂)— or —C(CH₃)₂CH₂CH₂—.
 42. The syntheticpolymer of claim 35 wherein “c” is
 0. 43. The synthetic polymer of claim35 wherein “d” is
 0. 44. The synthetic polymer of claim 35 wherein thependant group on Q₁ capable of forming hydrogen bonds is —CONH₂.
 45. Thesynthetic polymer of claim 35 wherein the pendant group on Q₁ capable offorming covalent bonds is —CONHCHOHCHO.
 46. The synthetic polymer ofclaim 35 wherein Q₁ has —CONH₂ and —CONHCHOHCHO pendant groups.
 47. Asynthetic polymer containing one or more aliphatic hydrocarbon moieties,said synthetic polymer having the following structure:

where: a, b>0; c,d≧0 such that c+d>0; w≧1; Q₁=a monomer unit or a blockor graft copolymer containing a pendant group capable of forminghydrogen or covalent bonds with cellulose; Q₂=a monomer unit or a blockor graft copolymer containing a C₈ or higher linear or branched,saturated or unsaturated, substituted or unsubstituted aliphatichydrocarbon moiety incorporated as part of the backbone of the syntheticpolymer; Q₃=a monomer unit or a block or graft copolymer containing acharge functionality; and Q₄=a monomer unit or a block or graftcopolymer containing a hydrophilic moiety, which is desirable for makingthe material into a form suitable for papermaking.
 48. The syntheticpolymer of claim 47 wherein Q₂ is a block copolymer of polymers selectedfrom the group consisting of polyethylene, polypropylene,polyisobutylene, and polytetrafluoroethylene.
 49. A synthetic polymercontaining one or more aliphatic hydrocarbon moieties, said syntheticpolymer having the following structure:

where: a, b>0; c,d≧0 such that c+d>0; w≧1; Q₁=a monomer unit or a blockor graft copolymer containing one or more pendant —CONHCHOHCHO groups;Q₂=a monomer unit or a block or graft copolymer containing a C₈ orhigher linear or branched, saturated or unsaturated, substituted orunsubstituted aliphatic hydrocarbon moiety incorporated as part of thebackbone of the synthetic polymer; Q₃=a monomer unit or a block or graftcopolymer containing a charge functionality; and Q₄=a monomer unit or ablock or graft copolymer containing a hydrophilic moiety, which isdesirable for making the material into a form suitable for papermaking.50. The synthetic polymer of claim 49 wherein Q₁ further contains apendant functionality selected from the group consisting of —CONH₂,—COOH, —COO⁻M⁺, —OH, and mixtures thereof, wherein M⁺ is a counter ion.51. A synthetic polymer containing one or more aliphatic hydrocarbonmoieties, said synthetic polymer having the following structure:

where: w≧1; R₁=H, C₁₋₄ alkyl; f, b>0; c, e, d>0; Q₂=a block or graftcopolymer containing a C₈ or higher linear or branched, saturated orunsaturated, substituted or unsubstituted aliphatic hydrocarbon moietyincorporated as part of the backbone of the synthetic polymer; Q₃=amonomer unit or a block or graft copolymer containing a chargefunctionality; and Q₄=a monomer unit or a block or graft copolymercontaining a hydrophilic moiety, which is desirable for making thematerial into a form suitable for papermaking.
 52. The polymer of claim31 wherein the Q₂ moiety is derived from polymerization of ethylene,propylene, perflouroethylene, isobutylene or mixtures thereof.
 53. Asynthetic polymer containing one or more aliphatic hydrocarbon moieties,said synthetic polymer having the following structure:

where: a, b>0; c,d>0 such that c+d>0; w≧1; Q₁=a monomer unit or a blockor graft copolymer containing one or more pendant —CONHCHOHCHO groups;Q₂=a monomer unit or a block or graft copolymer containing a C₈ orhigher linear or branched, saturated or unsaturated, substituted orunsubstituted aliphatic hydrocarbon moiety; Q₃=a monomer unit or a blockor graft copolymer containing a charge functionality; and Q₄=a monomerunit or a block or graft copolymer containing a hydrophilic moiety,which is desirable for making the material into a form suitable forpapermaking.
 54. The synthetic polymer of claim 53 wherein Q₁ furthercontains a pendant functinality selected from the group consisting of—CONH₂, —COOH, —COO⁻M⁺, —OH, and mixtures thereof, wherein M⁺ is acounter ion.
 55. A synthetic polymer containing one or more aliphatichydrocarbon moieties, said synthetic polymer having the followingstructure:

where: w≧1; R₁, R₂, R₃=H, C₁₋₄ alkyl; f, b>0; c, e≧0; R₄=Z₁—R₆—Y radicalwhere: Z₁=any radical capable of bonding the R₆ group to the polymer;R₆=any aliphatic, linear or branched, saturated or unsaturated,substituted or non-substituted hydrocarbon; Y=H, —N⁺R₇R₈R₉, —NR₇R₈,where R₇, R₈, R₉ are same or different and are H or C₁₋₃₀ linear orbranched, saturated or unsaturated aliphatic hydrocarbons and where atleast one of R₆, R₇, R₈, R₉ must be an aliphatic, linear or branched,substituted or non-substituted, hydrocarbon of chain length 8 or higher;R₅=Z₂—R₁₀—W; Z₂=any radical capable of bonding the R₁₀ group to thepolymer; R₁₀=any linear or branched, aliphatic or aromatic hydrocarbonof 2 or more carbons, preferably —(CH₂CH₂)—, —C(CH₃)₂CH₂CH₂—; andW=—N+R₁₁,R₁₂,R₁₃ where R₁₁, R₁₂, R₁₃ are C₁₋₄ alkyl groups.
 56. Thesynthetic polymer of claim 55 wherein Z₁ is selected from the groupconsisting of aryl, —CH₂—, —COO—, —CONH—, —O—, —S—, —OSO₂O—, —OOC— andmixtures thereof.
 57. The synthetic polymer of claim 55 wherein Z₂ isselected from the group consisting of aryl, —CH₂—, —COO—, —CONH—, —O—,—S—, —OSO₂O—, —OOC— and mixtures thereof.
 58. The synthetic polymer ofclaim 55 wherein R₁₀ is —(CH₂CH₂)— or —C(CH₃)₂CH₂CH₂—.
 59. A syntheticpolymer containing one or more aliphatic hydrocarbon moieties, saidsynthetic polymer having the following structure:

where: w≧1; R₁, R₂=H or C₁₋₄ alkyl; f, b, c>0; e≧0; R₄=Z₁—R₆—Y radicalwhere: Z₁=any radical capable of bonding the R₆ group to the polymer;R₆=any aliphatic, linear or branched, saturated or unsaturated,substituted or non-substituted hydrocarbon; and Y=H, —N⁺R₇R₈R₉, or—NR₇R₈, where R₇, R₈, R₉ are same or different and are H or C₁₋₃₀ linearor branched, saturated or unsaturated aliphatic hydrocarbons and whereat least one of R₆, R₇, R₈, R₉ must be an aliphatic, linear or branched,substituted or non-substituted, hydrocarbon of chain length 8 or higher.60. The synthetic polymer of claim 59 wherein Z₁ is selected from thegroup consisting of aryl, —CH₂—, —COO—, —CONH—, —O—, —S—, —OSO₂O—, —OOC—and mixtures thereof.